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Phosphine‐functionalized metal‐organic frameworks (P‐MOFs) as an emerging class of coordination polymers, have provided novel opportunities for the development of heterogeneous catalysts. Yet, compared with the ubiquitous phosphine systems in homogeneous catalysis, heterogenization of phosphines in MOFs is still at its early stage. In this Minireview, we summarize the synthetic strategies, characterization and catalytic reactions based on the P‐MOFs reported in literature. In particular, various catalytic reactions are discussed in detail in terms of phosphine ligand structure‐function relationship, including the potential obstacles for future development. Finally, we discuss the possible solutions, including new types of reactions and techniques as the perspectives for the development of P‐MOF catalysts, highlighting the opportunities and challenges. [ABSTRACT FROM AUTHOR]

To mitigate the greenhouse effect, a number of porous organic polymers (POPs) has been developed for carbon capture. Considering the permanent quadrupole of symmetrical CO2 molecules, the integration of electron-rich groups into POPs is a feasible way to enhance the dipole-quadrupole interactions between host and guest. To comprehensively explore the effect of pore environment, including specific surface area, pore size, and number of heteroatoms, on carbon dioxide adsorption capacity, we synthesized a series of microporous POPs with different content of β-ketoenamine structures via Schiff-base condensation reactions. These materials exhibit high BET specific surface areas, high stability, and excellent CO2 adsorption capacity. It is worth mentioning that the CO2 adsorption capacity and CO2/N2 selectivity of TAPPy-TFP reaches 3.87 mmol g-1 and 27. This work demonstrates that the introduction of β-ketoenamine sites directly through condensation reaction is an effective strategy to improve the carbon dioxide adsorption performance of carbon dioxide., (© 2024 Wiley‐VCH GmbH.)

2D van der Waals (vdW) magnets open landmark horizons in the development of innovative spintronic device architectures. However, their fabrication with large scale poses challenges due to high synthesis temperatures (>500 °C) and difficulties in integrating them with standard complementary metal-oxide semiconductor (CMOS) technology on amorphous substrates such as silicon oxide (SiO 2 ) and silicon nitride (SiN x ). Here, a seeded growth technique for crystallizing CrTe 2 films on amorphous SiN x /Si and SiO 2 /Si substrates with a low thermal budget is presented. This fabrication process optimizes large-scale, granular atomic layers on amorphous substrates, yielding a substantial coercivity of 11.5 kilo-oersted, attributed to weak intergranular exchange coupling. Field-driven Néel-type stripe domain dynamics explain the amplified coercivity. Moreover, the granular CrTe 2 devices on Si wafers display significantly enhanced magnetoresistance, more than doubling that of single-crystalline counterparts. Current-assisted magnetization switching, enabled by a substantial spin-orbit torque with a large spin Hall angle (85) and spin Hall conductivity (1.02 ×  10 7 ℏ/2e  Ω⁻¹  m⁻¹), is also demonstrated. These observations underscore the proficiency in manipulating crystallinity within integrated 2D magnetic films on Si wafers, paving the way for large-scale batch manufacturing of practical magnetoelectronic and spintronic devices, heralding a new era of technological innovation., (© 2024 The Authors. Advanced Materials published by Wiley‐VCH GmbH.)

While trinuclear [Fe x M 3- x (μ 3 -O)] cluster-based metal-organic frameworks (MOFs) have found wide applications in gas storage and catalysis, it is still challenging to identify the structure of open metal sites obtained through proper activations and understand their influence on the adsorption and catalytic properties. Herein, we use in situ variable-temperature single-crystal X-ray diffraction to monitor the structural evolution of [Fe x M 3- x (μ 3 -O)]-based MOFs (PCN-250, M = Ni 2+ , Co 2+ , Zn 2+ , Mg 2+ ) upon thermal activation and provide the snapshots of metal sites at different temperatures. The exposure of open Fe 3+ sites was observed along with the transformation of Fe 3+ coordination geometries from octahedron to square pyramid. Furthermore, the effect of divalent metals in heterometallic PCN-250 was studied for the purpose of reducing the activation temperature and increasing the number of open metal sites. The metal site structures were corroborated by X-ray absorption and infrared spectroscopy. These results will not only guide the pretreatment of [Fe x M 3- x (μ 3 -O)]-based MOFs but also corroborate spectral and computational studies on these materials.

Precise shaping of metal-organic frameworks (MOFs) is significant in both fundamental coordination chemistry and practical applications, such as catalysis, separation, and biomedicine. Herein, we demonstrated a linker scissoring strategy for precisely shaping MOFs through surface conformational pairing. In this strategy, the bidentate linkers which were designed according to the original tetratopic ligands and the coordination environment of MOF surfaces, were utilized as the covering agents. The shape of these covering agents and the surface conformation of metals onto MOFs restricted them to coordinate on specific MOF facets thus precisely controlling the shape of the MOFs. Different shapes of PCN-608 from nanoplate (PCN-NP) to nanorod (PCN-NR) have been targeted by adding different bidentate linkers. The universality of this strategy was demonstrated by controlling the shapes of the NU-MOFs from nanoplate to nanorod. This strategy provides a new guiding principle to synthesize MOF nanocrystals with controlled shapes., (© 2022 Wiley-VCH GmbH.)

The development of porous composite materials is of great significance for their potentially improved performance over those of individual components and extensive applications in separation, energy storage, and heterogeneous catalysis. Now mesoporous metal-organic frameworks (MOFs) with macroporous melamine foam (MF) have been integrated using a one-pot process, generating a series of MOF/MF composite materials with preserved crystallinity, hierarchical porosity, and increased stability over that of melamine foam. The MOF nanocrystals were threaded by the melamine foam networks, resembling a ball-and-stick model overall. The resulting MOF/MF composite materials were employed as an effective heterogeneous catalyst for the epoxidation of cholesteryl esters. Combining the advantages of interpenetrative mesoporous and macroporous structures, the MOF/melamine foam composite has higher dispersibility and more accessibility of catalytic sites, exhibiting excellent catalytic performance., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)